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Title: The influence of a presence of a heavy atom on the spin-spin coupling constants between two light nuclei in organometallic compounds and halogen derivatives

Abstract

The {sup 1}J{sub CC} and {sup 1}J{sub CH} spin-spin coupling constants have been calculated by means of density functional theory (DFT) for a set of derivatives of aliphatic hydrocarbons substituted with I, At, Cd, and Hg in order to evaluate the substituent and relativistic effects for these properties. The main goal was to estimate HALA (heavy-atom-on-light-atom) effects on spin-spin coupling constants and to explore the factors which may influence the HALA effect on these properties, including the nature of the heavy atom substituent and carbon hybridization. The methods applied range, in order of reduced complexity, from Dirac-Kohn-Sham method (density functional theory with four-component Dirac-Coulomb Hamiltonian), through DFT with two- and one-component Zeroth Order Regular Approximation (ZORA) Hamiltonians, to scalar non-relativistic effective core potentials with the non-relativistic Hamiltonian. Thus, we are able to compare the performance of ZORA-DFT and Dirac-Kohn-Sham methods for modelling of the HALA effects on the spin-spin coupling constants.

Authors:
;  [1]
  1. Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warszawa (Poland)
Publication Date:
OSTI Identifier:
22253590
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 140; Journal Issue: 2; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; APPROXIMATIONS; COUPLING CONSTANTS; DENSITY FUNCTIONAL METHOD; HALOGENS; HAMILTONIANS; HYBRIDIZATION; HYDROCARBONS; LIGHT NUCLEI; ORGANOMETALLIC COMPOUNDS; RELATIVISTIC RANGE; SIMULATION; SPIN

Citation Formats

Wodyński, Artur, and Pecul, Magdalena. The influence of a presence of a heavy atom on the spin-spin coupling constants between two light nuclei in organometallic compounds and halogen derivatives. United States: N. p., 2014. Web. doi:10.1063/1.4858466.
Wodyński, Artur, & Pecul, Magdalena. The influence of a presence of a heavy atom on the spin-spin coupling constants between two light nuclei in organometallic compounds and halogen derivatives. United States. https://doi.org/10.1063/1.4858466
Wodyński, Artur, and Pecul, Magdalena. 2014. "The influence of a presence of a heavy atom on the spin-spin coupling constants between two light nuclei in organometallic compounds and halogen derivatives". United States. https://doi.org/10.1063/1.4858466.
@article{osti_22253590,
title = {The influence of a presence of a heavy atom on the spin-spin coupling constants between two light nuclei in organometallic compounds and halogen derivatives},
author = {Wodyński, Artur and Pecul, Magdalena},
abstractNote = {The {sup 1}J{sub CC} and {sup 1}J{sub CH} spin-spin coupling constants have been calculated by means of density functional theory (DFT) for a set of derivatives of aliphatic hydrocarbons substituted with I, At, Cd, and Hg in order to evaluate the substituent and relativistic effects for these properties. The main goal was to estimate HALA (heavy-atom-on-light-atom) effects on spin-spin coupling constants and to explore the factors which may influence the HALA effect on these properties, including the nature of the heavy atom substituent and carbon hybridization. The methods applied range, in order of reduced complexity, from Dirac-Kohn-Sham method (density functional theory with four-component Dirac-Coulomb Hamiltonian), through DFT with two- and one-component Zeroth Order Regular Approximation (ZORA) Hamiltonians, to scalar non-relativistic effective core potentials with the non-relativistic Hamiltonian. Thus, we are able to compare the performance of ZORA-DFT and Dirac-Kohn-Sham methods for modelling of the HALA effects on the spin-spin coupling constants.},
doi = {10.1063/1.4858466},
url = {https://www.osti.gov/biblio/22253590}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 2,
volume = 140,
place = {United States},
year = {Tue Jan 14 00:00:00 EST 2014},
month = {Tue Jan 14 00:00:00 EST 2014}
}